CN112122621B - Preparation method of gold and silver bimetallic nanocluster capable of generating near-infrared electrochemiluminescence radiation - Google Patents
Preparation method of gold and silver bimetallic nanocluster capable of generating near-infrared electrochemiluminescence radiation Download PDFInfo
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- CN112122621B CN112122621B CN202011007487.8A CN202011007487A CN112122621B CN 112122621 B CN112122621 B CN 112122621B CN 202011007487 A CN202011007487 A CN 202011007487A CN 112122621 B CN112122621 B CN 112122621B
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Abstract
The invention belongs to the field of analytical technical methods, and relates to a preparation method of gold-silver bimetallic nanoclusters capable of generating near-infrared electrochemiluminescence radiation+And Ag+The water-soluble gold and silver bimetallic nanocluster is prepared by a principle method. The method has the advantages of easily obtained raw materials, good water solubility, simple synthesis device, mild conditions and safe operation. The gold and silver bimetallic cluster has good stability and can generate near infrared electrochemical luminescence with the maximum radiation wavelength larger than 850 nanometers.
Description
Technical Field
The invention belongs to the field of analysis technical methods, and relates to preparation of a water-soluble gold-silver bimetallic nanocluster capable of generating near-infrared electrochemiluminescence.
Background
Since the electrochemical luminescence of Si nanoparticles was first reported in 2002 by Bard group (Science 2002,296, 1293), a series of advances have been made in the electrochemical luminescence of quantum dot-based nanomaterials represented by II-VI quantum dots (chem. rev.2014,114, 11027). II-VI quantum dots typically contain toxic elements with potential environmental and biotoxic exposure risks. The electrochemical luminescence of gold, silver and copper metal nanoparticles with good biocompatibility is gaining wide attention. Yang and the like find that the electrochemical luminescence of the gold nanocluster can be obviously enhanced by forming a rigid conjugated structure on the surface of the metal nanocluster, the electrochemical luminescence of the prepared gold nanocluster is positioned in a visible light region, and the maximum radiation wavelength is 532 nanometers (Angew. chem. int.Ed.2019, 58 and 6901); liu et al found that by using a method of preparing gold and silver bimetallic nanoclusters, not only can the electrochemiluminescence of the gold nanoclusters in a visible light region be greatly enhanced, but also new strong ECL radiation related to surface defects can be generated in a near infrared region, and the maximum radiation wavelength of the gold and silver bimetallic nanoclusters is 710 nanometers (chem.
The research and development of the nano material with single-band electrochemical luminescence in the near infrared region have important value for developing the spectral research of the electrochemical luminescence and realizing the wider application of the electrochemical luminescence. Korean patent documents KR1020190142814A and KR102091221B1 disclose a water-soluble gold nanocluster having a single band of electrochemiluminescence radiation in the near infrared region with a maximum radiation wavelength around 800nm, respectively, and a method for preparing the same.
At present, no preparation method and technology for metal nanoclusters or quantum dots with maximum radiation wavelength of aqueous-phase electrochemiluminescence exceeding 850 nanometers exist. The research and development of related methods and technologies have important academic value for promoting the development of the long-wave region electrochemiluminescence system and further realizing the wave band regulation and control of electrochemiluminescence, and the application prospect is wide.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing water-soluble gold and silver bimetallic nanoclusters by using methionine as a stabilizing agent and a reducing agent. The gold and silver bimetallic nanocluster prepared by the method can generate near-infrared electrochemiluminescence in a long-wave region in a water phase system, the maximum emission wavelength of the gold and silver bimetallic nanocluster exceeds 850nm, and the maximum emission wavelength can reach 900nm under the optimal condition.
The technical scheme of the invention is as follows:
a preparation method of near-infrared electrochemiluminescence gold and silver bimetallic nanoclusters comprises the following steps:
au is reduced by methionine by taking chloroauric acid as a gold source, silver nitrate as a silver source and methionine as a reducing agent and a stabilizing agent+And Ag+And preparing the water-soluble gold and silver bimetallic nanocluster.
According to the invention, preferably, the preparation method of the near-infrared electrochemiluminescence gold and silver bimetallic nanocluster comprises the following steps:
(1) h is to be4AuCl4Solution with AgNO3Ultrasonically mixing the solution uniformly;
(2) adding a methionine solution into a sodium hydroxide solution for dissolving, and uniformly mixing by ultrasonic;
(3) uniformly mixing the solutions prepared in the steps (1) and (2), adjusting the pH value to 9.0-12.0, incubating at 37 ℃ for 6-10 hours, and centrifuging the obtained solution to remove large particles at the bottom; adding sulfuric acid solution into the supernatant, centrifuging, dissolving the obtained precipitate in ammonia water, and incubating at 70-90 deg.C for 10-30 min;
(4) and (4) centrifugally purifying the solution obtained in the step (3) by using isopropanol to obtain precipitate, namely the gold and silver bimetallic nanocluster.
According to the present invention, preferably, in step (1): silver molar ratio ═ 1-5: 1, more preferably 2: 1.
According to the invention, it is preferred that H in step (1)4AuCl4The concentration of the solution is 80-100mM, AgNO3The concentration of the solution is 5-15 mM.
According to the invention, it is preferred that methionine in step (2) is reacted with AgNO in step (1)3In a molar ratio of 5 to 25: 6, more preferably 20: 6.
according to the present invention, it is preferable that the pH of the mixed solution at the end of the step (3) is 11.0 to 12.0, further preferably 12.0;
preferably, the incubation time of the mixed solution after the pH adjustment is 8 to 10 hours, more preferably 10 hours.
According to the present invention, it is preferable that the sulfuric acid solution in the step (3) has a concentration of 98 wt%. Adding sulfuric acid to precipitate the initially prepared gold-silver bimetallic nano-ions.
Preferably, the concentration of the aqueous ammonia is 2 wt%.
According to the present invention, a preferred mixed solution is Au: Ag: methionine-20: 10: and 3, when the pH value is 12, the prepared nanocluster can reach 900nm in electrochemiluminescence wavelength.
According to the invention, a preferred embodiment of the preparation method of the near-infrared electrochemiluminescence gold and silver bimetallic nanocluster comprises the following steps:
(1) 0.085g AgNO3(purity 99.8%) in 50mL of ultrapure water to prepare 10mM AgNO3A solution; 1.0g H4AuCl4·3H2Preparation of 96mM H by dissolving O (purity 99%) in 26mL of ultrapure water4AuCl4A solution; 2.038g NaOH (96% purity) was dissolved in 50mL of ultrapure water to prepare a 1M NaOH stock solution; 2.715mL H2SO4(concentrated sulfuric acid concentration 98 wt.%) was dissolved in 50mL of ultrapure water to prepare 1M H2SO4A solution; 2mL NH3·H2O (concentration 20 wt% -25 wt%) dissolved in 25mL of ultrapure water to prepare 2wt% NH3·H2O solution for use；
0.25mL of 96mM H4AuCl4The solution is mixed with 0.5-2.4mL of 10mM AgNO3Ultrasonically mixing the solution uniformly;
(2) weighing methionine and AgNO in step (1)3In a molar ratio of 5: 6-25: 6, adding 0.3mL of 1M sodium hydroxide for dissolution, and uniformly mixing by ultrasonic waves;
(3) uniformly mixing the solutions prepared in the steps (2) and (3), adjusting the pH value to 9.0-12.0, incubating for 6-10 hours at 37 ℃, centrifuging the prepared solution at 5000 rotation speed, and removing large particles at the bottom; adding 0.5 mL of 1M sulfuric acid solution into the supernatant, centrifuging at 8000 rpm, dissolving the obtained precipitate in 3mL of 2% ammonia water, and incubating in an oven at 80 ℃ for 20 minutes;
(4) and (4) centrifugally purifying the solution obtained in the step (3) by using isopropanol to obtain precipitate, namely the gold and silver bimetallic nanocluster.
The invention has the beneficial effects that:
1. the gold and silver nanocluster prepared by the method has the advantages of no toxic elements, good biological affinity and stable storage.
2. The method has the advantages of simple steps, mild conditions and safe operation. Can generate single-band electrochemiluminescence radiation in a near infrared region in an aqueous phase system, and the maximum radiation wavelength of the electrochemiluminescence radiation is more than 850 nanometers and can reach 900nm under the optimal condition.
Drawings
Fig. 1 is an X-ray diffraction spectrum of the gold and silver bimetallic nanoclusters fabricated in example 1.
Fig. 2 is an X-ray energy spectrum analysis spectrum of the gold and silver bimetallic nanoclusters manufactured in example 2.
Fig. 3 is a high power transmission electron micrograph of the gold and silver bimetallic nanoclusters fabricated in example 3.
Fig. 4 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters manufactured in example 4.
Fig. 5 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters manufactured in example 5.
Fig. 6 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters manufactured in example 6.
Fig. 7 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters manufactured in example 7.
Fig. 8 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 8.
Fig. 9 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 9.
Fig. 10 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 10.
Fig. 11 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 11.
Fig. 12 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 12.
Fig. 13 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 13.
Fig. 14 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 14.
Fig. 15 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 15.
Fig. 16 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 16.
Fig. 17 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 17.
Fig. 18 is a fluorescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 18.
Fig. 19 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 19.
Fig. 20 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 20.
Fig. 21 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 21.
Fig. 22 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 22.
Fig. 23 is an ultraviolet spectrum of the gold and silver bimetallic nanoclusters fabricated in example 23.
Fig. 24 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 24.
Fig. 25 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 25.
Fig. 26 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 26.
Fig. 27 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 27.
Fig. 28 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 28.
Fig. 29 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 29.
Fig. 30 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 30.
Fig. 31 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 31.
Fig. 32 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 32.
Fig. 33 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 33.
Fig. 34 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 34.
Fig. 35 is a photograph of the gold and silver bimetallic nanoclusters produced in example 35.
Fig. 36 is a photograph of gold and silver bimetallic nanoclusters fabricated in example 36.
Fig. 37 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters manufactured in example 37.
Fig. 38 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters manufactured in example 38.
Fig. 39 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 39.
Fig. 40 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 40.
Fig. 41 is a total electrochemiluminescence spectrum of the gold and silver bimetallic nanoclusters fabricated in example 41.
Fig. 42 is a graph of the total electrochemiluminescence spectrum of the gold nanoclusters manufactured in comparative example 1.
FIG. 43 is a diagram showing a total electrochemiluminescence spectrum of gold nanoclusters manufactured in comparative example 2.
FIG. 44 is a graph showing the total electrochemiluminescence spectrum of gold nanoclusters manufactured in comparative example 3.
Fig. 45 is a photograph of the gold and silver bimetallic nanoclusters manufactured in comparative example 4. The metal cluster can not be prepared because of the sedimentation in the synthesis process.
Fig. 46 is a total electrochemiluminescence spectrum of the gold and silver bimetal nanoclusters manufactured in comparative example 5.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
The fluorescence spectrogram of the gold and silver nanoclusters in the embodiment is acquired by an WGY-10 type fluorescence spectrophotometer, the ultraviolet-visible light absorption spectrum is acquired by a TU-1901 series ultraviolet-visible spectrophotometer, and the electrochemical luminescence spectrum is acquired by an electrochemical luminescence spectrum acquisition system constructed by the patent technology ZL 201620300698.3 of detection system capable of accurately acquiring electrochemiluminescence spectrum information. The system realizes spectrum collection by combining a Versa STAT 3 type electrochemical analyzer and an Acton SP-2300 type CCD grating spectrometer, wherein the potential window is 0-1.6V, and the scanning speed is 50 millivolts per second. In the electrochemical luminescence test, a glassy carbon electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt wire is used as a counter electrode, and a gold-silver nanocluster modified electrode is prepared by a method of dripping 10 microliters of 1mg/ml gold-silver nanocluster solution on the surface of the working electrode and drying; the test solution was a 0.1 mol/l phosphoric acid buffer solution (pH 7.4) containing triethanolamine at a concentration of 10 mmol/l; the electrochemiluminescence spectrum collected is the integrated spectrum of all ECL radiation.
Example 1
All the vessels were soaked with freshly prepared aqua regia for 24 hours, thoroughly rinsed with ultrapure water and ethanol, and then air-dried
(1) 0.085g AgNO3(99.8%) Ag stock solution (10mM) was prepared in 50mL of ultrapure water; 1g H4AuCl4·3H2Dissolving O (99%) in 26mL of ultrapure water to obtain an Au stock solution (96 mM); 2.038g NaOH (96%) was dissolved in 50mL of ultrapure water to prepare a stock solution of NaOH (1M); 2.715mL H2SO4(concentrated sulfuric acid 98%) was dissolved in 50mL of ultrapure water to prepare an aqueous ammonia stock solution (2%).
(2) 0.25mL of Au solution was ultrasonically mixed with 1.2mL of Ag solution.
(3) 0.40mM methionine was weighed and dissolved by adding 0.3mL of 1M sodium hydroxide, and mixed by sonication.
(4) And 2, 3, uniformly mixing the solutions prepared in the steps, adjusting the pH value to be 12.0, incubating for 10 hours at 37 ℃, centrifuging the finally prepared solution for 5000 revolutions to remove large particles at the bottom, adding 0.5 mL of 1M sulfuric acid solution, centrifuging at 8000 revolutions to remove supernatant, adding 3mL of 2% ammonia water into the precipitate obtained by final centrifugation, and incubating for 20 minutes at 80 ℃ in an oven.
(5) Finally, the prepared quantum dots are centrifuged by isopropanol at 13300 revolutions to collect powder, and the powder is ground and tested for an X-ray diffraction spectrum.
Example 2
The procedure is as in example 1, except that the powder is collected centrifugally and ground before testing the X-ray spectral analysis.
Example 3
The procedure was the same as in example 1, except that the powder was collected by centrifugation and 1mg/mL solution prepared from the powder was dropped on a copper mesh to characterize the morphology of nanoclusters.
Example 4
The procedure was as in example 1, except that the pH of the mixed solution in the step (4) was 9.
Example 5
The procedure was as in example 1, except that the pH of the mixed solution in the step (4) was 10.
Example 6
The procedure was as in example 1, except that the pH of the mixed solution in the step (4) was 10.5.
Example 7
The procedure was as in example 1, except that the pH of the mixed solution in the step (4) was 11.
Example 8
The procedure is as in example 1, except that the assay is fluorescence.
Example 9
The procedure is as in example 4, except that the test method is UV.
Example 10
The procedure is as in example 5, except that the test method is UV.
Example 11
The procedure is as in example 6, except that the test method is UV.
Example 12
The procedure is as in example 7, except that the test method is UV.
Example 13
The procedure is as in example 8, except that the test method is UV.
Example 14
The procedure is as in example 1, except that 0.48mL of silver nitrate is added in step (2).
Example 15
The procedure is as in example 1, except that 0.6mL of silver nitrate is added in step (2).
Example 16
The procedure is as in example 1, except that 0.8mL of silver nitrate is added in step (2).
Example 17
The procedure is as in example 1, except that the assay is fluorescence.
Example 18
The procedure is as in example 1, except that 2.4mL of silver nitrate is added in step (2).
Example 19
The procedure is as in example 15, except that the test method is UV.
Example 20
The procedure is as in example 16, except that the test method is UV.
Example 21
The procedure is as in example 17, except that the test method is UV.
Example 22
The procedure is as in example 18, except that the test method is UV.
Example 23
The procedure is as in example 19, except that the test method is UV.
Example 24
The test method is an electrochemiluminescence spectroscopy test of a three-electrode system and no quantum dots are added.
Example 25
The procedure is as in example 14, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 26
The procedure is as in example 15, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 27
The procedure is as in example 16, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 28
The procedure is as in example 17, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 29
The procedure is as in example 18, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 30
The procedure is as in example 4, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 31
The procedure is as in example 5, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 32
The procedure is as in example 6, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 33
The procedure is as in example 7, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 34
The procedure is as in example 8, except that the test method is CV-driven electrochemiluminescence spectroscopy.
Example 35
The procedure is as in example 1, except that methionine is added in the step (3) and AgNO is added in the step (1)3In a molar ratio of 10: 6.
example 36
The procedure is as in example 1, except that methionine is added in the step (3) and AgNO is added in the step (1)3In a molar ratio of 15: 6.
example 37
The procedure is as in example 1, except that methionine is added in the step (3) and AgNO is added in the step (1)3In a molar ratio of 20: 6.
example 38
The procedure is as in example 1, except that methionine is added in the step (3) and AgNO is added in the step (1)3In a molar ratio of 25: 6.
example 39
The procedure was as in example 1, except that the incubation time of the mixed solution at 37 ℃ in step (4) was 6 hours.
Example 40
The procedure was as in example 1, except that the incubation time of the mixed solution at 37 ℃ in step (4) was 8 hours.
EXAMPLE 41
The procedure was as in example 1, except that the incubation time of the mixed solution at 37 ℃ in step (4) was 10 hours.
Comparative example 1
According to Chem Commun 2020; 56,5580, the wavelength of Au nanocluster synthesized by taking cyclodextrin as ligand is 790nm, and is not more than 850 nm.
Comparative example 2
The procedure is as in example 1, except that in step (3), silver nitrate is added in an amount of 0mL, and the wavelength is 800nm and does not exceed 850 nm.
Comparative example 3
The procedure was as in example 1, except that 0mL of chloroauric acid was added in step (3), and no electrochemical spectrum was observed.
Comparative example 4
The procedure is as in example 1, methionine is reacted with AgNO from step (1)3In a molar ratio of 5: 6, precipitation phenomenon appears, and the quantum dots are not successfully synthesized.
Comparative example 5
The procedure was as in example 1 except that the pH of the mixed solution in the step (4) was 7, methionine was not dissolved, and electrochemiluminescence was weak.
Claims (7)
1. A preparation method of near-infrared electrochemiluminescence gold and silver bimetallic nanoclusters comprises the following steps:
(1) h is to be4AuCl4Solution with AgNO3The solution is mixed evenly by ultrasonic, and gold: silver molar ratio = (1-5): 1;
(2) adding a methionine solution into a sodium hydroxide solution for dissolving, and uniformly mixing by ultrasonic;
(3) the solution prepared in the steps (1) and (2) is mixed with the solution prepared in the step (1) according to the methionine in the step (2) and the AgNO in the step (1)3In a molar ratio of 10 to 25: 6, uniformly mixing, adjusting the pH value to 9.0-12.0, incubating for 6-10 hours at 37 ℃, and then centrifuging the obtained solution to remove large particles at the bottom; adding sulfuric acid solution into the supernatant, centrifuging, dissolving the obtained precipitate in ammonia water, and incubating at 70-90 deg.C for 10-30 min;
(4) and (4) centrifugally purifying the solution obtained in the step (3) by using isopropanol to obtain precipitate, namely the gold and silver bimetallic nanocluster.
2. The preparation method of the near-infrared electrochemiluminescence gold-silver bimetallic nanoclusters according to claim 1, wherein in the step (1): silver molar ratio =2: 1.
3. The method for preparing near-infrared electrochemiluminescence gold and silver bimetallic nanoclusters according to claim 1, wherein in the step (1), H is4AuCl4The concentration of the solution is 80-100mM, AgNO3The concentration of the solution is 5-15 mM.
4. The method for preparing near-infrared electrochemiluminescence gold and silver bimetallic nanoclusters according to claim 1, wherein methionine in step (2) and AgNO in step (1)3In a molar ratio of 20: 6.
5. the method for preparing near-infrared electrochemiluminescence gold and silver bimetallic nanoclusters according to claim 1, wherein the pH value of the final mixed solution in the step (3) is 11.0-12.0.
6. The method for preparing a near-infrared electrochemiluminescence gold and silver bimetallic nanocluster according to claim 1, wherein the incubation time of the mixed solution after the pH value is adjusted in the step (3) is 8-10 hours.
7. The method for preparing a near-infrared electrochemiluminescence gold and silver bimetallic nanocluster according to claim 1, wherein the concentration of the sulfuric acid solution in the step (3) is 98wt%, and the concentration of the ammonia water is 2 wt%;
and (3) after the solution in the step (3) is uniformly mixed, adding Ag, methionine = 20: 10: 3, molar ratio; the pH was 12.
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| CN110116219A (en) * | 2019-04-28 | 2019-08-13 | 尹跃超 | A kind of method that green quickly prepares gold-silver alloy nano particle |
| CN110016043A (en) * | 2019-05-10 | 2019-07-16 | 西北工业大学 | A kind of gold nano cluster and preparation method thereof with transmitting white light property |
| CN110129484A (en) * | 2019-06-05 | 2019-08-16 | 济南大学 | A method of influenza A virus is detected based on Doré metal nanocluster enhancing fluorescence combination ring mediated isothermal amplification |
| CN110508828A (en) * | 2019-08-28 | 2019-11-29 | 淮北师范大学 | The preparation method of fluorescent red-orange copper nanocluster based on l-methionine |
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